Hydrofining process for hydrocarbon-containing feed streams

Abstract

At least one decomposable compound of a metal selected from the group consisting of copper, zinc and the metals of Group III-B, Group IV-B, Group VB, Group VIB, Group VIIB and Group VIII of the Periodic Table is mixed with a hydrocarbon-containing feed stream. The hydrocarbon-containing feed stream containing such decomposable compound is then contacted with a suitable refractory inorganic material to reduce the concentration of metals, sulfur and Ramsbottom carbon residue contained in the hydrocarbon-containing feed stream. The suitable refractory inorganic material may also be slurried with the hydrocarbon-containing feed stream.

What is claimed is: 
     
       1. A process for hydrofining a hydrocarbon-containing feed stream comprising the steps of: introducing a suitable quantity of a suitable decomposable compound of a metal selected from the group consisting of copper and the metals of Group V-B, Group VI-B, Group VII-B and Group VIII of the Periodic Table into said hydrocarbon-containing feed stream; and   contacting said hydrocarbon-containing feed stream containing said decomposable compound under suitable hydrofining conditions with hydrogen and a suitable refractory inorganic material, wherein the concentration of transition metals selected from the group consisting of the metals of copper and Group V-B, Group VI-B, Group VII-B and Group VIII of the Periodic Table in said refractory inorganic material is less than about 1 weight-%, based on the weight of said refractory inorganic material, when said refractory inorganic material is initially contacted with said hydrocarbon-containing feed stream, and wherein said decomposable compound is selected from the group consisting of carbonyls and dithiocarbamates.   
     
     
       2. A process in accordance with claim 1 wherein said decomposable compound is selected from the group consisting of molybdenum hexacarbonyl and molybdenum dithiocarbamate. 
     
     
       3. A process in accordance with claim 1 wherein a sufficient quantity of said decomposable compound is added to said hydrocarbon-containing feed stream to result in a concentration of the metal in said decomposable compound in said hydrocarbon feed stream in the range of about 1 to about 600 ppm. 
     
     
       4. A process in accordance with claim 1 wherein a sufficient quantity of said decomposable compound is added to said hydrocarbon-containing feed stream to result in a concentration of the metal in said decomposable compound in said hydrocarbon feed stream in the range of about 2 to about 100 ppm. 
     
     
       5. A process in accordance with claim 1 wherein said refractory inorganic material has a surface area in the range of about 10 to about 500 m 2  /g and a pore volume in the range of about 0.1 to about 3.0 cc/g. 
     
     
       6. A process in accordance with claim 1 wherein said refractory inorganic material has a surface area in the range of about 20 to about 300 m 2  /g and a pore volume in the range of about 0.3 to about 1.5 cc/g. 
     
     
       7. A process in accordance with claim 1 wherein said refractory inorganic material is selected from the group consisting of silica, metal oxides, metal silicates, chemically combined metal oxides, metal phosphates and mixtures of any two or more thereof. 
     
     
       8. A process in accordance with claim 7 wherein said refractory inorganic material is selected from the group consisting of alumina, silica, silica-alumina, aluminosilicates, P 2  O 5  -alumina, B 2  O 3  -alumina, magnesium oxide, calcium oxide, lanthanium oxide, cerium oxides, thorium dioxide, titanium dioxide, titania-alumina, zirconium dioxide, aluminum phosphate, magnesium phosphate, calcium phosphate, cerium phosphate, thorium phosphate, zirconium phosphate, zinc phosphate, zinc aluminate and zinc titanate. 
     
     
       9. A process in accordance with claim 8 wherein said refractory metal oxide contains about 95 weight-% alumina based on the weight of said refractory metal oxide. 
     
     
       10. A process in accordance with claim 8 wherein said refractory metal oxide contains about 97 weight-% alumina based on the weight of said refractory metal oxide. 
     
     
       11. A process in accordance with claim 8 wherein said refractory inorganic material is zinc titanate. 
     
     
       12. A process in accordance with claim 8 wherein said refractory inorganic material is zinc aluminate. 
     
     
       13. A process in accordance with claim 1 wherein said suitable hydrofining conditions comprise a reaction time between said refractory inorganic material and said hydrocarbon-containing feed stream in the range of about 0.1 hour to about 10 hours, a temperature in the range of 150° C. to about 550° C., a pressure in the range of about atmospheric to about 10,000 psig and a hydrogen flow rate in the range of about 100 to about 20,000 standard cubic feet per barrel of said hydrocarbon-containing feed stream. 
     
     
       14. A process in accordance with claim 1 wherein said suitable hydrofining conditions comprise a reaction time between said refractory inorganic material and said hydrocarbon-containing feed stream in the range of about 0.4 hours to about 4 hours, a temperture in the range of 350° C. to about 450° C., a pressure in the range of about 500 to about 3,000 psig and hydrogen flow rate in the range of about 1,000 to about 6,000 standard cubic feet per barrel of said hydrocarbon-containing feed stream. 
     
     
       15. A process in accordance with claim 1 wherein said hydrofining process is a demetallization process and wherein said hydrocarbon-containing feed stream contains metals. 
     
     
       16. A process in accordance with claim 15 wherein said metals are nickel and vanadium. 
     
     
       17. A process in accordance with claim 1 wherein said hydrofining process is a desulfurization process and wherein said hydrocarbon-containing feed stream contains organic sulfur compounds. 
     
     
       18. A process in accordance with claim 19 wherein said organic sulfur compounds are selected from the group consisting of sulfides, disulfides, mercaptans, thiophenes, benzylthiophenes, and dibenzylthiophenes. 
     
     
       19. A process in accordance with claim 1 wherein said hydrofining process is a process for removing Ramsbottom carbon residue and wherein said hydrocarbon-containing feed stream contains Ramsbottom carbon residue. 
     
     
       20. A process in accordance with claim 2 wherein said decomposable compound is molybdenum hexacarbonyl. 
     
     
       21. A process in accordance with claim 2 wherein said decomposable compound is molybdenum dithiocarbamate. 
     
     
       22. A process for hydrofining a hydrocarbon-containing feed stream comprising the steps of: introducing a suitable quantity of a suitable decomposable compound of a metal selected from the group consisting of copper, zinc and the metals of Group III-B, Group IV-B, Group V-B, Group VI-B, Group VII-B and Group VIII of the Periodic Table into said hydrocarbon-containing feed stream; and   contacting said hydrocarbon-containing feed stream containing said decomposable compound under suitable hydrofining conditions with hydrogen and a suitable refractory inorganic material, wherein the concentration of transition metals selected from the group consisting of the metals of copper, zinc and Group III-B, Group IV-B, Group V-B, Group VI-B, Group VII-B and Group VIII of the Periodic Table in said refractory inorganic material is less than about 1 weight-%, based on the weight of said refractory inorganic material, when said refractory inorganic material is initially contacted with said hydrocarbon-containing feed stream, and wherein said suitable decomposable compound is selected from the group consisting of carbonyls, dithiocarbamates and dithiophosphates.   
     
     
       23. A process in accordance with claim 22 wherein said decomposable compound is selected from the group consisting of molybdenum hexacarbonyl, molybdenum dithiocarbamate and molybdenum dithiophosphate. 
     
     
       24. A process in accordance with claim 22 wherein a sufficient quantity of said decomposable compound is added to said hydrocarbon-containing feed stream to result in a concentration of the metal in said decomposable compound in said hydrocarbon feed stream in the range of about 1 to about 600 ppm. 
     
     
       25. A process in accordance with claim 22 wherein a sufficient quantity of said decomposable compound is added to said hydrocarbon-containing feed stream to result in a concentration of the metal in said decomposable compound in said hydrocarbon feed stream in the range of about 2 to about 100 ppm. 
     
     
       26. A process in accordance with claim 22 wherein said refractory inorganic material has a surface area in the range of about 10 to about 500 m 2  /g and a pore volume in the range of about 0.1 to about 3.0 cc/g. 
     
     
       27. A process in accordance with claim 22 wherein said refractory inorganic material has a surface area in the range of about 20 to about 300 m 2  /g and a pore volume in the range of about 0.3 to about 1.5 cc/g. 
     
     
       28. A process in accordance with claim 22 wherein said refractory inorganic material is selected from the group consisting of silica, metal oxides, metal silicates, chemically combined metal oxides, metal phosphates and mixtures of any two or more thereof. 
     
     
       29. A process in accordance with claim 28 wherein said refractory inorganic material is selected from the group consisting of alumina, silica, silica-alumina, aluminosilicates, P 2  O 5  -alumina, B 2  O 3  -alumina, magnesium oxide, calcium oxide, lanthanium oxide, cerium oxides, thorium dioxide, titanium dioxide, titania-alumina, zirconium dioxide, aluminum phosphate, magnesium phosphate, calcium phosphate, cerium phosphate, thorium phosphate, zirconium phosphate, zinc phosphate, zinc aluminate and zinc titanate. 
     
     
       30. A process in accordance with claim 29 wherein said refractory metal oxide contains about 95 weight-% alumina based on the weight of said refractory metal oxide. 
     
     
       31. A process in accordance with claim 29 wherein said refractory metal oxide contains about 97 weight-% alumina based on the weight of said refractory metal oxide. 
     
     
       32. A process in accordance with claim 29 wherein said refractory inorganic material is zinc titanate. 
     
     
       33. A process in accordance with claim 29 wherein said refractory inorganic material is zinc aluminate. 
     
     
       34. A process in accordance with claim 22 wherein said suitable hydrofining conditions comprise a reaction time between said refractory inorganic material and said hydrocarbon-containing feed stream in the range of about 0.1 hour to about 10 hours, a temperature in the range of 150° C. to about 550° C., a pressure in the range of about atmospheric to about 10,000 psig and a hydrogen flow rate in the range of about 100 to about 20,000 standard cubic feet per barrel of said hydrocarbon-containing feed stream. 
     
     
       35. A process in accordance with claim 22 wherein said suitable hydrofining conditions comprise a reaction time between said refractory inorganic material and said hydrocarbon-containing feed stream in the range of about 0.4 hours to about 4 hours, a temperature in the range of 350° C. to about 450° C., a pressure in the range of about 500 to about 3,000 psig and hydrogen flow rate in the range of about 1,000 to about 6,000 standard cubic feet per barrel of said hydrocarbon-containing feed stream. 
     
     
       36. A process in accordance with claim 22 wherein said hydrofining process is a demetallization process and wherein said hydrocarbon-containing feed stream contains metals. 
     
     
       37. A process in accordance with claim 36 wherein said metals are nickel and vanadium. 
     
     
       38. A process in accordance with claim 22 wherein said hydrofining process is a desulfurization process and wherein said hydrocarbon-containing feed stream contains organic sulfur compounds. 
     
     
       39. A process in accordance with claim 38 wherein said organic sulfur compounds are selected from the group consisting of sulfides, disulfides, mercaptans, thiophenes, benzylthiophenes, and dibenzylthiophenes. 
     
     
       40. A process in accordance with claim 22 wherein said hydrofining process is a process for removing Ramsbottom carbon residue and wherein said hydrocarbon-containing feed stream contains Ramsbottom carbon residue. 
     
     
       41. A process in accordance with claim 23 wherein said decomposable compound is molybdenum dithiophosphate. 
     
     
       42. A process for hydrofining a hydrocarbon-containing feed stream comprising the steps of: introducing a suitable quantity of a suitable decomposable compound of a metal selected from the group consisting of copper, zinc and the metals of Group III-B, Group IV-B, Group V-B, Group VI-B, Group VII-B and Group VIII of the Periodic Table and a suitable refractory inorganic material into said hydrocarbon-containing feed stream to form a slurry; and   contacting said slurry under suitable hydrofining conditions with hydrogen in a reactor, wherein the concentration of transition metals selected from the group consisting of the metals of copper, zinc and Group III-B, Group IV-B, Group V-B, Group VI-B, Group VII-B and Group VIII of the Periodic Table in said refractory inorganic material is less than about 1 weight-%, based on the weight of said refractory inorganic material, when said refractory inorganic material is initially introduced into said hydrocarbon-containing feed stream, and wherein said suitable decomposable compound is selected from the group consisting of carbonyls, dithiocarbamates and dithiophosphates.   
     
     
       43. A process in accordance with claim 42 wherein said decomposable compound is selected from the group consisting of molybdenum hexacarbonyl, molybdenum dithiocarbamate and molybdenum dithiophosphate. 
     
     
       44. A process in accordance with claim 42 wherein a sufficient quantity of said decomposable compound is added to said hydrocarbon-containing feed stream to result in a concentration of the metal in said decomposable compound in said slurry in the range of about 1 to about 600 ppm. 
     
     
       45. A process in accordance with claim 42 wherein a sufficient quantity of said decomposable compound is added to said hydrocarbon-containing feed stream to result in a concentration of the metal in said decomposable compound in said slurry in the range of about 2 to about 100 ppm. 
     
     
       46. A process in accordance with claim 42 wherein said refractory inorganic material has a surface area in the range of about 10 to about 500 m 2  /g and a pore volume in the range of about 0.1 to about 3.0 cc/g. 
     
     
       47. A process in accordance with claim 42 wherein said refractory inorganic material has a surface area in the range of about 20 to about 300 m 2  /g and a pore volume in the range of about 0.3 to about 1.5 cc/g. 
     
     
       48. A process in accordance with claim 48 wherein said refractory inorganic material is selected from the group consisting of silica, metal oxides, metal silicates, chemically combined metal oxides, metal phosphates and mixtures of any two or more thereof. 
     
     
       49. A process in accordance with claim 48 wherein said refractory inorganic material is selected from the group consisting of alumina, silica, silica-alumina, aluminosilicates, P 2  O 5  -alumina, B 2  O 3  -alumina, magnesium oxide, calcium oxide, lanthanium oxide, cerium oxides, thorium dioxide, titanium dioxide, titania-alumina, zirconium dioxide, aluminum phosphate, magnesium phosphate, calcium phosphate, cerium phosphate, thorium phosphate, zirconium phosphate, zinc phosphate, zinc aluminate and zinc titanate. 
     
     
       50. A process in accordance with claim 49 wherein said refractory metal oxide is silica. 
     
     
       51. A process in accordance with claim 42 wherein said suitable hydrofining conditions comprise a reaction time in said reactor for said slurry in the range of about 0.1 hour to about 10 hours, a temperature in the range of 150° C. to about 550° C., a pressure in the range of about atmospheric to about 10,000 psig and a hydrogen flow rate in the range of about 100 to about 20,000 standard cubic feet per barrel of said slurry. 
     
     
       52. A process in accordance with claim 51 wherein said suitable hydrofining conditions comprise a reaction time is said reactor for said slurry in the range of about 0.4 hours to about 4 hours, a temperture in the range of 350° C. to about 450° C., a pressure in the range of about 500 to about 3,000 psig and hydrogen flow rate in the range of about 1,000 to about 6,000 standard cubic feet per barrel of said slurry. 
     
     
       53. A process in accordance with claim 42 wherein said hydrofining process is a demetallization process and wherein said hydrocarbon-containing feed stream contains metals. 
     
     
       54. A process in accordance with claim 53 wherein said metals are nickel and vanadium. 
     
     
       55. A process in accordance with claim 42 wherein said hydrofining process is a desulfurization process and wherein said hydrocarbon-containing feed stream contains organic sulfur compounds. 
     
     
       56. A process in accordance with claim 55 wherein said organic sulfur compounds are selected from the group consisting of sulfides, disulfides, mercaptans, thiophenes, benzylthiophenes, and dibenzylthiophenes. 
     
     
       57. A process in accordance with claim 42 wherein said hydrofining process is a process for removing Ramsbottom carbon residue and wherein said hydrocarbon-containing feed stream contains Ramsbottom carbon residue. 
     
     
       58. A process in accordance with claim 43 wherein said decomposable compound is molybdenum hexacarbonyl. 
     
     
       59. A process in accordance with claim 43 wherein said decomposable compound is molybdenum dithiocarbamate. 
     
     
       60. A process in accordance with claim 43 wherein said decomposable compound is molybdenum dithiophosphate.